Novel esters

ABSTRACT

Acetates of the formula ##STR1## wherein X 1  represents hydrogen, halogen or C 1  -C 4  alkyl, X 2  represents hydrogen or halogen, and Y represents hydrogen, halogen or methyl, processes for their manufacture and a method of controlling pests which comprises the use of these compounds.

The present invention relates to acetates, processes for theirmanufacture and a method of controlling pests which comprises the use ofthese compounds.

The acetates have the formula ##STR2## wherein X₁ represents hydrogen,halogen or C₁ -C₄ alkyl, X₂ represents hydrogen or halogen, and Yrepresents hydrogen, halogen or methyl.

By halogen is meant in this connection fluorine, chlorine, bromine oriodine, especially fluorine, chlorine or bromine.

Suitable alkyl groups represented by X₁ are: methyl, ethyl, propyl,isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.

Preferred compounds on account of their action are those of the formulaI, wherein X₁ represents hydrogen, chlorine, bromine or methyl, X₂represents hydrogen or chlorine, and Y represents hydrogen, p-fluorine,p-chlorine, p-bromine or p-methyl.

Particularly preferred compounds, however, are those of the formula I,wherein X₁ represents hydrogen or p-chlorine, X₂ represents hydrogen,and Y represents hydrogen, p-fluorine, p-chlorine, p-bromine orp-methyl.

The compounds of the formula I are obtained by methods which are knownper se, for example as follows: ##STR3##

In the formulae II to IV, X₁, X₂ and Y are as defined for formula I.

In the formulae III and IV, X represents a halogen atom, especially achlorine or bromine atom, and in formula VI R represents C₁ -C₄ alkyl,especially methyl or ethyl.

Suitable acid acceptors for processes 1 and 2 are in particular tertiaryamines, such as trialkylamine and pyridine, and also hydroxides, oxides,carbonates and bicarbonates of alkali metals and alkaline earth metals,and in addition alkali metal alcoholates, for example potassiumtert-butylate and sodium methylate. As hydrophilic agent for process 3,dicyclohexylcarbodiimide can be used for example. Processes 1 to 4 arecarried out at a reaction temperature between -10° and 120° C., usuallybetween 20° and 80° C., under normal or elevated pressure and preferablyin an inert solvent or diluent. Examples of suitable solvents ordiluents are: ether and ethereal compounds, for example diethyl ether,dipropyl ether, dioxane, dimethoxyethane and tetrahydrofurane; amides,such as N,N-dialkylated carboxamides; aliphatic, aromatic andhalogenated hydrocarbons, especially benzene, toluene, xylenes,chloroform and chlorobenzene; nitriles, such as acetonitrile; dimethylsulfoxide; and ketones, such as acetone and methyl ethyl ketone.

The starting materials of the formulae II to VII are known or they canbe prepared by methods analogous to known ones.

The compounds of the formula I are in the form of a mixture of differentoptically active isomers if individual optically active startingmaterials are not used in the reaction. The different isomer mixturescan be separated into the individual isomers by known methods. Thecompound of the formula I is to be understood as comprising both theindividual isomers and the mixtures thereof. The compounds of theformula I are suitable for controlling a variety of animal and plantpests. In particular, the compounds of the formula I are suitable forcontrolling insects, phytopathogenic mites and ticks, for example of theorders: Lepidoptera, Coleoptera, Homoptera, Heteroptera, Diptera,Acarina, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga,Thysanura, Isoptera, Psocoptera and Hymenoptera.

In particular, the compounds of the formula I are suitable forcontrolling insects which are harmful to plants, especially insectswhich damage plants by eating, in ornamentals and crops of usefulplants, especially in cotton plantations (e.g. Spodoptera littoralis andHeliothis virescens) and in vegetable crops (for example Leptinotarsadecemlineata and Myzus persicae).

The active compounds of the formula I also have a very good actionagainst flies, for example Musca domestica and mosquito larvae.

The acaricidal and/or insecticidal action can be substantially broadenedand adapted to prevailing circumstances by addition of otherinsecticides and/or acaricides. Examples of suitable additives include:organic phosphorus compounds, nitrophenols and derivatives thereof,formamidines, ureas, pyethroids, carbamates, and chlorinatedhydrocarbons.

Compounds of the formula I are also combined with particular advantagewith substances which exert a synergistic or potentiating effect onpyrethroids. Examples of such compounds include: piperonyl butoxide,propynyl ether, propynyl oximes, propynyl carbamates and propynylphosphates, 2-(3,4-methylenedioxyphenoxy)-3,6,9-trioxaundecane (Sesamexor Sesoxane), S,S,S-tributylphosphorotrithioate,1,2-methylenedioxy-4(2-(octylsulfinyl)-propyl)-benzene.

The compounds of the formula I may be used as pure active substance ortogether with suitable carriers and/or adjuvants. Suitable carriers andadjuvants can be solid or liquid and correspond to the substancesconventionally used in the art of formulation, for example natural orregenerated substances, solvents, dispersants, wetting agents,tackifiers, thickeners, binders and/or fertilisers.

The compositions of the present invention are manufactured in knownmanner by homogeneously mixing and/or grinding active substances of theformula I with the suitable carriers, with or without the addition ofdispersants or solvents which are inert to the active substances.

The compounds of the formula I may be processed to the followingformulations:

Solid formulations:

Dusts, tracking powders and granules (coated granules, impregnatedgranules and homogeneous granules).

Liquid formulations:

(a) active substances which are dispersable in water: wettable powders,pastes and emulsions;

(b) solutions.

The content of active substance in the above described compositions isgenerally between 0.1% and 95%, though concentrations of up to 99.5% oreven pure active substance can also be used if the compositions areapplied from an aircraft or other appropriate application devices.

The compounds (active substances) of the formula I can, for example, beformulated as follows (throughout the present specification all partsand percentages are by weight):

Dusts

The following substances are used to formulate

(a) a 5% and (b) a 2% dust:

(a) 5 parts of active substance,

95 parts of talc;

(b) 2 parts of active substance,

1 part of highly disperse silicic acid,

97 parts of talc.

The active substance is mixed with the carriers and ground.

Granules

The following substances are used to formulate 5% granules:

5 parts of active substance

0.25 parts of epichlorohydrin,

0.25 parts of cetyl polyglycol ether,

3.50 parts of polyethylene glycol,

91 parts of kaolin (particle size 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin and the mixture isdissolved in 6 parts of acetone; the polyethylene glycol and cetylpolyglycol ether are then added. The resultant solution is sprayed onkaolin, and the acetone is subsequently evaporated in vacuo.

Wettable powders:

The following constituents are used to formulate

(a) a 40%, (b) and (c) a 25%, and (d) a 10% wettable powder:

(a) 40 parts of active substance,

5 parts of sodium dibutylnaphthalenesulfonate,

54 parts of silicic acid.

(b) 25 parts of active substance,

4.5 parts of calcium ligninsulfonate,

1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1),

1.5 parts of sodium dibutylnaphthalenesulfonate,

19.1 parts of silicic acid,

19.5 parts of Champagne chalk,

28.1 parts of kaolin,

(c) 25 parts of active substance,

2.5 parts of isooctylphenoxy-polyoxyethyleneethanol,

1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1),

8.3 parts of sodium aluminium silicate,

16.5 parts of kieselguhr,

46 parts of kaolin;

(d) 10 parts of active substance,

3 parts of a mixture of the sodium salts of saturated fatty alcoholsulfates,

5 parts of naphthalenesulphonic acid/formaldehyde condensate,

82 parts of kaolin.

The active substances are homogeneously mixed with the additives insuitable mixers and the mixture is then ground in appropriate mills androllers. Wettable powders are obtained which can be diluted with waterto give suspensions of the desired concentration.

Emulsifiable concentrates:

The following substances are used to formulate (a) a 10%, (b) a 25% and(c) a 50% emulsifiable concentrate:

(a) 10 parts of active substance,

3.4 parts of epoxidised vegetable oil,

3.4 parts of a combination emulsifier consisting of fatty alcoholpolyglycol ether and alkylarylsulfonates calcium salt,

40 parts of dimethyl formamide,

43.2 parts of xylene;

(b) 25 parts of active substance,

2.5 parts of epoxidised vegetable oil,

10 parts of alkylarylsulfonate/fatty alcohol polyglycol ether mixture,

5 parts of dimethyl formamide,

57.5 parts of xylene;

(c) 50 parts of active substance,

4.2 parts of tributylphenol-polyglycol ether,

5.8 parts of cylcium dodecylbenzenesulfonate,

20 parts of cyclohexanene,

20 parts of xylene.

By diluting these concentrates with water it is possible to obtainemulsions of the required concentration.

Sprays:

The following ingredients are used to formulate (a) a 5% spray, and (b)a 95% spray:

(a) 5 parts of active substance,

1 part of epichlorohydrin,

94 parts of ligroin (boiling range 160°-190° C.);

(b) 95 parts of active substance,

5 parts of epichlorohydrin.

The invention is further illustrated by the following Examples.

EXAMPLE 1 (a) Manufacture of α-prop-1-ynyl-3-phenoxybenzyl alcohol

To a solution of 8 g of methyl acetylene in 100 ml of tetrahydrofuraneis slowly added at 0° C. a Grignard solution freshly prepared from 4 gofmagnesium and 20 g of ethylene bromide in 20 ml of tetrahydrofurane.Themixture is stirred for 15 minutes under argon and a solution of 27 gof p-phenoxybenzaldehyde in 100 ml of tetrahydrofurane is added dropwiseat 0° to 5° C. After stirring for 14 hours at room temperature,thereaction mixture is cooled to 0° C. with 50 g of ice and, after the slowaddition of 25 ml of conc. hydrochloric acid, extracted with ether. Theethereal extract is washed twice with water and twice with saturatedsodium chloride solution, dried over sodium sulfate, filtered andconcentrated. The product is chromatographed over silica gel with ethylacetate/hexane (1:4) as eluant, affording the compound of the formula##STR4##with a refractive index of n_(D) ²⁰° =1.5898.

(b) Manufacture ofα-prop-1-ynyl-3-phenoxybenzyl-α-isopropyl-4-chlorophenylacetate

A solution of 4 g of α-prop-1-ynyl-3-phenoxybenzyl alcohol in 20 ml oftoluene is added dropwise at 0° C. to a solution of 3.88 g ofα-isopropyl-4-chlorophenylacetyl chloride and 1.8 ml of pyridine in 50ml of toluene. The reaction mixture is stirred for 14 hours at roomtemperature, then diluted with ether, washed once with water, once with2 N hydrochloric acid, three times with saturated sodium chloridesolution, dried over sodium sulfate and concentrated. The product ischromatographedover silica gel with ether/hexane (1:3) as eluant,affording the compound of the formula ##STR5##in the form of adiastereoisomer mixture with a refractive index of n_(D) ²⁰° =1.5671.

The following compounds are also prepared in analogous manner: ##STR6##

EXAMPLE 2 Insecticidal stomach poison action

Cotton plants were sprayed with a 0.05% aqueous emulsion of activesubstance (obtained from a 10% emulsifiable concentrate). After thespray coating had dried, the cotton plants were populated with larvae ofSpodoptera littoralis and Heliothis virescens in the L₃ -stage. The testwas carried out at 24° C. and 60% relative humidity.

In this test, the compounds of Example 1 exhibited a good insecticidalstomach poison action against Spodoptera and Heliothis larvae.

EXAMPLE 3 Acaricidal action

Twelve hours before the test for acaricidal action, Phaseolus vulgarisplants were populated with an infested piece of leaf from a mass cultureof Tetranychus urticae. The mobile stages which had migrated to theplantswere sprayed with the emulsified test preparations from achromatography atomiser in such a way that the spray broth did not runoff. The number ofliving and dead larvae, adults and eggs was evaluatedunder a stereoscopic microscope after 2 and 7 days and the resultexpressed in percentage values. During the test run, the plants stood ingreenhouse compartments at 25° C.

In this test, the compounds of Example 1 acted against adults, larvaeand eggs of Tetranychus urticae.

EXAMPLE 4 Action against ticks

(A) Rhipicephalus bursa Five adult ticks and 50 tick larvae were countedinto each of a number of test tubes and immersed for 1 to 2 minutes in 2ml of an aqueous emulsion containing a concentration of 100, 10, 1 or0.1 ppm of test substance. Each test tube was then sealed with acotton-wool plug and placed on its head to enable the cotton wool toabsorb the activesubstance emulsion. Evaluation of the action againstadults was made after 2 weeks and of that against larvae after 2 days.Each test was repeated twice.

(B) Boophilus microplus (larvae) Test were carried out with 20OP-sensitiveand 20 OP-resistant larvae using aqueous emulsions similarto those used inTest A. (The resistance refers to the tolerance towardsdiazinone). The compounds of Example 1 acted in these tests againstadults and larvae of Rhipicephalus bursa and OP-sensitive andOP-resistant larvae of Boophilus microplus.

What is claimed is:
 1. An acetate of the formula ##STR7## wherein X₁represents hydrogen, halogen or C₁ -C₄ alkyl, X₂ represents hydrogen orhalogen, and Y represents hydrogen, halogen or methyl.
 2. A compoundaccording to claim 1, wherein X₁ represents hydrogen, chlorine, bromineor methyl, X₂ represents hydrogen or chlorine, and Y representshydrogen, p-fluorine, p-chlorine, p-bromine or p-methyl.
 3. A compoundaccording to claim 2, wherein X₁ represents hydrogen or p-chlorine, X₂represents hydrogen, and Y represents hydrogen, p-fluorine, p-chlorine,p-bromine or p-methyl.
 4. The compound according to claim 3 of theformula ##STR8##
 5. The compound according to claim 3 of the formula##STR9##
 6. A pesticidal composition which contains, as activecomponent, a compound according to claim 1 and suitable carriers and/orother adjuvants.
 7. A method of controlling animal and plant pests whichcomprises the use of a compound according to claim
 1. 8. A methodaccording to claim 7, wherein the pests to be controlled are insects andrepresentatives of the order Acarina.